Condensation of chlorobenzene and formaldehyde to polymeric oils



United States Patent 3,0284% 1 CONDENSATEQN 0F CilLQlROElEl-NZENE AND FOEMALDEHYDE T0 POLYMERIC OILS John W. Schick, Delaware Township, Camden County,

sulfuric acid to chlorobenzene varying between about 0.1

and about 0.4; at a temperature varying between about 60 C. and about 130 C.; and for a period of time varying between about one hour and about 6 hours.

NJ., assigns! to Socony Mobil Oil Company, Inc, a THE REACTANTS corporation of New York 0 fl gle No 3, 1 13 Noh5 The reactants used in the process of this invention are 4 Ufiimsv, chlorobenzene and formaldehyde. Chlorobenzene (mono- This invention is concerned with the condensation of chlclobfinlene p lf chloflde) 1s 21 l known aromatic'ccmpounds with formaldehyde. It is more par- Compound a 18 y avallable F y- It ticulariy concerned with a process for condensing chlorocan be used techmcal grade, but SubSlaPUauY Pllra benzene and formaldehyde to fo m almost l i l chlorobenzene is preferred. Chlorobenzene 18 produced polymer il by methods well known 1n'the art, such as by catalytic As is well known to those familiar with the art, it has ichlormatiofi of benzenebeen proposed to condense aromatic hydrocarbons, such The folmaldehyde reactant can be the p lf as benzene, or phenols with formaldehyde to produce formaldehyde, pa r (p r y m the high molecular weight resinous materials. -Generally, 9 of the cychc f i lrlOXane- M dllute P' acidic clay catalysts have been suificient. in the case (10115 of formaldehyflei 511911 as are less of chlorobenzene as the aromatic compound reactant, able, bfifiallse y tend to (mute the strellgth of the however, the condensation with formaldehyde appears 2O Sulfuric acid Catalyst 9 Y 111 its VaYIQl-IS forms to be hindered so that yields are relatively low, in the 18 Wall known and feadlly available commefclallypresence of clay catalysts. The use of more drastic cata- STANDARD RUN PROCEDURE 1 sts and conditions leads to the formation of resinous pioducts for the most part In all the runs described and discussed hereln, the fol- Oily low molecular weight polymers of chlorobenzene 25 lowmgftandard procedure was used: d h b and formaldehyde are highly desirable as special solvents, A mlfimre parafqrmaldehyde c m as insecticides, and as secondary plasticizers for poly- E deslred. g ratio was Placid m a lleaction vinylchloride resins. Particularly suitable oils would be {he Sulfur; acld catalyst was added to i mixture at mixtures of bis(chlorophenyl) Ethane (dimer) and rate whereby the temperature of the reaction mixture was bis(chlorobenzyl) chlorobenzene (trimer). In this mamtamed below 69 Afer anthe surfunc f li connection it is highly desirable to be able to produce lyst had added the temperature of the reaction such a mixture of dimer and trimer to the substantial ture was raised to i run temperature (usually exclusion of higher molecular weight, resinous products. i and mammmed i g level for des1r.ed It has now been fmmd that an oily polymm. can be reaction tlme. After the reaction time, the reaction mixmade simply and economically. It has been discovered fi was PerPmted to Stand to Settle Into twolayersl that chlorobenzeneand formaldehyde can be condensed 1m 9 and layer mmoved and the orgilmc layjcr to produce a mixture of dimer and trimer to the substan- Was fitered through filtering P to remove .resldual i tial exclusion of higher molecular weight and resinous a W en, the (grgamc layer was sub ected to (118- product tillation. Unreacted chiorobenzene was stripped, and the Accordingly, it is a broad object of this invention to 40 r'emamdmL of the Organic l W fractloqated Into provide a process for producing useful polymer oils. mree fractlolnswnamelyi dlmer )the 3 f ,9' Another object is to provide a process for condensing phenyl) 640660 cut H (or mnler chlorobenzene and formaldehyde to produce an oily polythe g ff y f lOrObenZene-BP. 850-870 F., mer with low production of resinous polymer. A specific and a b msmous hlgher polymer object is to provide a process for producing a mixture EFFECT OF REACTION TEMPERATURE of bis(chlorophenyl) methane and bis(chlorobenzyl) Exam le 1 Thrau h 7 chlorobenzene to the substantial exclusion of higher p s g molecular Weight, resinous polymers. Other objects and Using the standard run procedure, a series of runs, advantages of this invention will become apparent to at several catalyst concentrations, were made in which those skilled in the art from the following detailed de the temperature was varied. The pertinent run data and scriptio'n. yield-s of these runs are set forth in Table I.

TABLE I Charge, grams Yield, grains Yield, Temp. Time weight Example 0. hrs. percent Chloro- HrSO Weight Paraiorrn Weight Cutl Cut2 Residue Total chlorobenzenc ratio ratio benzene 1 500 50 0. 10 00 0. 12 100 a 134 41 s 180 30. 0 2 500 50 0. 10 00 0.12 130 a 147 47 10 210 42. 0 3 500 100 0. 20 e0 0. 12 00 5 146 33 44 44. s 4. 500 100 0. 20 e0 0. 12 100 3 115 33 203' 40. c o 500 100 0.20 0.12 130 3 14s 7 s5 17 220 44.0 c 500 200 0. to 60 0.12 100 s 145 04 23 232 40.4 7 500 200 0. 40 00 0. 12 130 a .109 52 21 242 48. 4

In general, the present invention provides a process From the data in Table I, it will be noted that good for producing a polymer oil, that comprises reacting yields dimer and trimer product are obtained at temformaldehyde with chlorobenzene, in a weight ratio of peratures of 100-130 C. The upper limit of the tem formaldehyde to chlorobenzene varying between about perature range is set by the reflux temperature of chloro- 0.08 and about 0.2; in the presence of sulfuric acid catabenzene (132 (3.). Good yields of product were oblyst, the acid strength of said sulfuric acid being at least percent H 80 by weight, and the weight ratio of said tained, however, at 60 C. (Example 3) using a compensating longer reaction time, although somewhat more higher polymer was produced. Accordingly, the process of this invention can be carried out at temperatures varying between about 60 C. and about 130 C. Preferred reaction temperatures are between about 100 C. and about 130 C. 7

EFFECT OF REACTION TIME Examples 8 Through 14 Using the standard run procedure, series of runs were aoaaeae 4 CATALYST TO CHLOROBENZENE RATIO Examples 15 Through 17 Using the standard run procedure, a series of runs were made at 100 C. and at 130 C. In these runs, the amount of sulfuric acid catalyst (98 percent H 80 was varied to afford a variation of catalyst to cholorbenzene weight ratio. Pertinent run data and yields of these runs are set forth in Table HI. For comparison, data for made at the preferred temperatures, but using various 10 Examples 1, 2, 6, and 14 are also set forth in Table III.

TABLE 111 Charge, grams Yield, grams Yield,

Term, Time, weight.

Example 0. hrs. percent Ohloro- H2804 Weight Paraiorm Weight 7 Out 1 Cut 2 Residue Total chlorobenzcne ratio ratio benzene reaction times. Pertinent run data and yields of these runs are set forth in Table II. For purposes of completing the time comparison, data for Examples 1 and 4 are also included in Table II.

From the data in Table 111, it will be noted that yields increase with increased catalyst-chlorobenzene weight ratio to a maximum yield at 100 C. at a ratio of about 0.15, and at. 130 C. at a ratio of about 0.20. In general,

TABLE II Charge, grams Yield, grams Yield, Temp, Time, weight Example 0. hrs. percent Ghloro- H2804 Weight Paraforrn Weight Cut 1 Out 2 Residue Total clilorobenzene ratio ratio benzene From the data in Table 11, it will be noted that maxi- 45 the catalyst to chlorobenzene Weight ratio will be between temperature, will vary between about one hour and about 6 hours, and preferably between about 3 hours and about 6 hours.

about 0.10 and about 0.40, and preferably between about 0.10 and about 0.25.

FORMALDEHYDE CONCENTRATION Examples 18 Through 25 Using the standard run procedure, a series of runs was made at 100 C. and 130 C., using catalyst-chlorobenzene weight ratios of 0.10 and 0.20. In these runs, the amount of paraform was varied to give a range of formaldehyde to chlorobenzcne weight ratios. Pertinent run data and results of these runs are set forth in Table IV.

For comparison, data for Examples 1, 2, 4, and 14 are also set forth in Table IV.

TABLE IV Charge, grams Yield, grams Yield, Temp., Time, weight Example 0. hrs. percent Chloro- H180 Weight Paraform W eight Cut 1 Out 2 Residue Total chlorobenzene ratio ratio benzene From the data in Table IV, it will be noted that yields increase with increase of formaldehyde-chlorobenzene ratio. However, utilization of the formaldehyde decreased with increased ratio. Generally, the formalde- Example 29 A run was made that was identical to that of Example 5, except that the formaldehyde was in the form of the cyclic trimer, tr-ioxane. There was a conversion hyde to chlorobenzene weight ratio will be between about f 501 i h percent, as compared to 44 wgight 0.08 and about 0.20, and preferably between about 0.10 cent in Example 5. Dimer and trimer product yields and 0.15. were of the same order of magnitude.

ACID STRENGTH Although the present invention has been described Examples 26 and 27 with preferred embodiments, it-is to be understood that modifications and variations may be resorted to, wlthout Using the Standard Tun Procedure, runs were made in departing from the spirit and scope of this invention, which sulfuric acid catalysts of varying strength were as those skilled in the art will readily understand. Such used. Pertinent run data and yields, in comparison with variations and modifications are considered to be withdata for Examples 13, are set forth in Table V. in the purview and scope of the appended claims.

TABLE V Charge, grams Yield, grams Yield, Temp., Time, weight Example 0. hrs. percent Chloro- H1804 Weight Paratorm Weight Out 1 Out2 Residue Total chlorobenzene ratio ratio benzene 500 1 100 0. 60 0.12 130 4 205 78 12 295 59. 0 500 2 100 0. 20 60 0. 12 130 3 188 66 12 266 as. 2 500 a 100 0. 20 60 0. 12 130 3 13s 44 10 192 38. 4

1 E2304. 2 9 H2304. 3 80.0% H2804. From the data of Table V, it is noted that maximum What is claimed is: conversion occurred using 98 weight percent sulfuric acid. 1. A process for producing a polymer oil, that com- When the acid strength was decreased, yield decreased, prises reacting formaldehyde with chlorobenzene, in a but even using 80 percent sulfuric acid was satisfactory. weight ratio of formaldehyde to chlorobenzene varying In general, the strength of the sulfuric acid catalyst can between about 0.08 and about 0.2; in the presence of be between about 80 percent and about 100 percent. In sulfuric acid catalyst, the acid strength of said sulfuric preferred practice the acid strength should be between acid being at least 80 percent H 80 by weight, and the about 94 percent and about 100 percent. weight ratio of said sulfuric acid to chlorobenzene vary- INCREMENTAL ADDITION OF FORMALDEHYDE ing between about 0.1 and about 0.4; at a temperature In the standard run procedure, sulfuric acid was added glarymg about 5 and z 130 g to a mixture containing all the chlorobenzene and form- 0 me varymg e Ween a on one our an aldehyde. If, however, the formaldehyde is added pora g d l th tionwise, i.e., by incremental addition, to a mixture of F W g E g O1 at p hlorobenzene and sulfuric acid catalyst definite ield inpn-ses (mm c y 6 wt 6 Orobanzene a c y weight ratio of formaldehyde to chlorobenzene varying creases can be reallzed. Th1s 1s lllustrated 111 the followbetween about 01 and about 015; in the presence mg example sulfuric acid catalyst, the acid strength of said sulfuric Example 28 acid being between about 94 percent and about 100 A mixture 500 grams f chlorobenzene and 100 percent H by weight, and the weight ratio of said grams T3110) 0f 98 Pereellt Sulfllfle acld catalyst sulfuric acid to chlorobenzene varying between about were Placed in a reaction Vessel- During a reaction P 0.1 and about 0.25; at a temperature varying between 0d of 3 hours, at grams Tatio) P about 100 C. and about 130 C.; and for a period of formaldehyde were added in five P Q the time varying between about three hours and about six addition being at one-half hour intervals. Separation of 50 h acid and the recovery of Products Were carried out as 3. The process defined in claim 1 wherein said formdescrihed in Standard F1111 p The Pertinent aldehyde is added portionwise to said chlorobenzene and run data and results, in comparison with Example 4, are id lf i id, Set forth in Table 4. The process defined in claim 2 wherein said form- TABLE VI Charge, gram-S Yield, grams Yield, Temp., Time, weight Example 0. hrs. ercent Chloro- H2804 Weight Paraform Weight Cutl Cut2 Residue Total chlorobenzene ratio ratio benzene 2s 500 100 0.20 4 500 o 0. 0 '60 i i 3 iii 2% Si 33% 2313 1 Added in five 12 gram portions.

It is to be noted that the conversion is increased b some 50 percent, when the process is carried out using incremental addition of formaldehye. There is, however, some increase in the amount of resinous polymer. In practice, the choice of method of reaction, whether standard or by incremental addition, will be governed by the desirability of greater conversion or of lower production of resinous products.

F ORM ALDEYDE As has been mentioned hereinbefore, forms of formaldehyde other than paraformaldehyde can be used.

1 Added in one portion using standard procedure.

y aldehyde is added portionwise to said chlorobenzene and said sulfuric acid.

References Cited in the file of this patent UNITED STATES PATENTS 2,548,982 Kemp Apr. 17, 1951 2,854,493 Fetterly Sept. 30, 1958 2,937,212 Breier et al. May 17, 1960 OTHER REFERENCES Stephen et al.: I. Chem. Soc., 117, 518-9, (1920). 

1. A PROCESS FOR PRODUCING A POLYMER OIL, THAT COMPRISES REACTING FORMALDEHYDE WITH CHLOROBHENZENE, IN A WEIGHT RATIO OF FROMALDEHYDE TO CHLOROBENZENE VARYING BETWEEN ABOUT 0.08 AND ABOUT 0.2; IN THE PRESENCE OF SULFURIC ACID CATALYST, THE ACID STRENGTH OF SAID SULFURIC ACID BEING AT LEAST 80 PERCENT H2SO4 BY WEIGHT, AND THE WEIGHT RATIO OF SAID SULFURIC ACID TO CHLOROBENZENE VARYING BETWEEN ABOUT 0.1 AND ABOUT 0.4; AT A TEMPERATURE VARYING BETWEEN ABOUT 60*C. AND ABOUT 130*C.; AND FOR A PERIOD OF TIME VARYING BETWEEN ABOUT ONE HOUR AND ABOUT SIX HOURS. 